DE951717C - Process for the production of thionothiol-phosphoric acid triesters - Google Patents

Process for the production of thionothiol-phosphoric acid triesters

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Publication number
DE951717C
DE951717C DEF13503A DEF0013503A DE951717C DE 951717 C DE951717 C DE 951717C DE F13503 A DEF13503 A DE F13503A DE F0013503 A DEF0013503 A DE F0013503A DE 951717 C DE951717 C DE 951717C
Authority
DE
Germany
Prior art keywords
production
thionothiol
phosphoric acid
acid triesters
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
DEF13503A
Other languages
German (de)
Inventor
Dr Gerhard Schrader
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Priority to DEF13503A priority Critical patent/DE951717C/en
Application granted granted Critical
Publication of DE951717C publication Critical patent/DE951717C/en
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/165—Esters of thiophosphoric acids
    • C07F9/1651—Esters of thiophosphoric acids with hydroxyalkyl compounds with further substituents on alkyl

Description

Zierfahren zur Herstellung von Thiono-thiol-phosphorsäuretriestern Nach dem Verfahren der deutschen Patentschrift 830 5o8 werden Ester der Thiophosphorsäure dadurch erhalten, daß man DialkylphosphorsäuTechloride mit Alkalisalzen von Mercaptanen der allgemeinen Formel H S-alkyl-S-R (R = aliphatischer, aromatischer oder araliphatischer Rest) in einem inerten Lösungsmittel umsetzt. Diese Verbindungen sind durch wertvolle insektizide Eigenschaften ausgezeichnet.Zierverfahren for the production of thionothiol-phosphoric acid triesters According to the process of the German patent specification 830 508, esters of thiophosphoric acid are obtained by dialkylphosphoric acid chlorides with alkali salts of mercaptans of the general formula H S-alkyl-SR (R = aliphatic, aromatic or araliphatic radical) Reacts in an inert solvent. These compounds are distinguished by valuable insecticidal properties.

Aus der deutschen Patentschrift Big 998 ist es weiter unter anderem bekannt, Carbaminyläthylthiono-thiolphosphorsäureester durch Reaktion von Salzen von Dialkyl-dithiophosphorsäusen mit Halogencarbonsäureamiden herzustellen. Es wurde nun gefunden, daß man zu hochwirksamen Insektiziden gelangt, wenn man O, O-Dialkylthiophosphorsäurechloride mit ß-aminosubstituierten aliphatischen Mercaptanen umsetzt.From the German patent specification Big 998 it is also known, inter alia, to produce carbaminylethylthionothiolphosphoric acid esters by reacting salts of dialkyldithiophosphoric acids with halocarboxamides. It has now been found that highly effective insecticides are obtained if O, O-dialkylthiophosphoric acid chlorides are reacted with β-amino-substituted aliphatic mercaptans.

Die erfindungsgemäß erhältlichen Verbindungen zeichnen sich durch eine erheblich gesteigerte Wirksamkeit gegenüber bekannten Verbindungen ähnlicher Zusammensetzung aus.The compounds obtainable according to the invention are distinguished by a significantly increased effectiveness compared to known compounds similar Composition from.

Die Umsetzung der O, O-Dialkylthiophosphorsäurechloride mit den genannten ß-aminosubstituierten arliphatischen Mercaptanen wird zweckmäßig in einem inerten Lösungsmittel bei mäßig erhöhter Temperatur in Gegenwart von säurebindenden Mitteln vorgenommen. Als Säurebindemittel haben sich getrocknete, feingepulverte Alkalicarbonate bewährt. Man kann aber auch die Alkalisalze der genannten Mercaptane direkt mit den O, O-Dialkylthiophosphorsäurechloriden reagieren lassen. Als inerte Lösungsmittel kommen Kohlenwasserstoffe, wie Benzol und Toluol, aber auch Ketone, z. B. Methyläthylketon, in Frage. Die neuen Thiono-thiolphosphorsäuretriester zeichnen sich bei guter insektizider Wirkung durch geringe toxische Wirkungen bei Warmblütern aus. Beispiel 133 g ß-Mercaptoäthyl-diät!hylamin (Journal of the American Chemical Society 67, S. I223) läßt man zu einer Anschlämmung von 23 g staubfeinem Natrium in 30o ccm Benzol bei 35 bis 45° unter Rühren tropfen. Nach dem Lösen des Natriums gibt man bei 5o° igo g O, O-Diäthyl-thiophosphorsäurechlorid unter Rühren hinzu. Man hält noch 3 Stunden auf 30°, saugt dann das entstandene Kochsalz ab und fraktioniert das Filtrat. Es werden igo g eines gelben, wasserunlöslichen Öles erhalten. Ausbeute 61 °!o der Theorie. Das O, O-Diäthyl-S-(fl-diäthylamino-ätäyl)-thiono-thiolphosphat siedet unter einem Druck von x mm bei z36°.The reaction of the O, O-dialkylthiophosphoric acid chlorides with the ß-amino-substituted arliphatic mercaptans mentioned is expediently carried out in an inert solvent at a moderately elevated temperature in the presence of acid-binding agents. Dried, finely powdered alkali carbonates have proven effective as acid binders. However, the alkali salts of the mercaptans mentioned can also be reacted directly with the O, O-dialkylthiophosphoric acid chlorides. Inert solvents are hydrocarbons, such as benzene and toluene, but also ketones, e.g. B. methyl ethyl ketone in question. The new thionothiolphosphoric acid triesters are characterized by good insecticidal effects and low toxic effects in warm-blooded animals. EXAMPLE 133 g of β-mercaptoethyl diethylamine (Journal of the American Chemical Society 67, p. I223) are added dropwise to a suspension of 23 g of dusty sodium in 30 ° cc of benzene at 35 ° to 45 ° with stirring. After the sodium has dissolved, O, O-diethyl-thiophosphoric acid chloride is added at 50 ° igo with stirring. It is kept at 30 ° for a further 3 hours, then the sodium chloride formed is filtered off with suction and the filtrate is fractionated. Igo g of a yellow, water-insoluble oil are obtained. Yield 61% of theory. The O, O-diethyl-S- (fl-diethylamino-ethyl) -thiono-thiolphosphate boils under a pressure of x mm at z36 °.

Claims (1)

PATENTANSPRUCH: Verfahren zur Herstellumg von Thiono-thiolphosphorsäuaretriestern nach Patent 83o 5o8, dadurch gekennzeichnet, daB O, O-Dialkylthiophosphorsäurechloride mit ß-aminosubstituierten aliphatischen Mercaptanen umgesetzt werden. In Betracht gezogene Druckschriften: Deutsche Patentschriften Nr. 830 508, &19 998, g33 807, 847 897, 876 691, 848 o44 864 252; USA.-Patentschriften Nr. 2 266 514, 2 630 45 1. PATENT CLAIM: Process for the production of thionothiolphosphoric acid triesters according to patent 83o 508, characterized in that O, O-dialkylthiophosphoric acid chlorides are reacted with ß-amino-substituted aliphatic mercaptans. Considered publications: German Patent Nos. 830 508, & 19 998, g33 807, 847 897, 876 691, 848 o44 864 252; USA. Patent Nos. 2,266,514, 2,630 45 1.
DEF13503A 1953-12-19 1953-12-19 Process for the production of thionothiol-phosphoric acid triesters Expired DE951717C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DEF13503A DE951717C (en) 1953-12-19 1953-12-19 Process for the production of thionothiol-phosphoric acid triesters

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEF13503A DE951717C (en) 1953-12-19 1953-12-19 Process for the production of thionothiol-phosphoric acid triesters

Publications (1)

Publication Number Publication Date
DE951717C true DE951717C (en) 1956-10-31

Family

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Family Applications (1)

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DEF13503A Expired DE951717C (en) 1953-12-19 1953-12-19 Process for the production of thionothiol-phosphoric acid triesters

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DE (1) DE951717C (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1032247B (en) * 1954-12-04 1958-06-19 Bayer Ag Process for the production of organic phosphorus compounds
DE1089376B (en) * 1958-02-12 1960-09-22 Bayer Ag Process for the preparation of thiophosphoric acid esters or thiophosphonic acid esters

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2266514A (en) * 1938-09-09 1941-12-16 American Cyanamid Co Esters of dithiophosphoric acids
DE819998C (en) * 1948-02-04 1951-11-08 American Cyanamid Co Process for the preparation of esters of phosphoric or thiophosphoric acid
DE830508C (en) * 1950-05-24 1952-02-04 Bayer Ag Process for the preparation of neutral esters of thiophosphoric acid
DE833807C (en) * 1948-03-26 1952-03-13 American Cyanamid Co Process for the preparation of dithiophosphoric acid triesters
DE847897C (en) * 1950-03-02 1952-08-28 American Cyanamid Co Process for the preparation of dithiophosphoric acid triesters
DE848041C (en) * 1949-07-13 1952-09-01 Borchers A G Geb Process for the preparation of esters of orthophosphoric acid and thiophosphoric acid
DE864252C (en) * 1950-05-06 1953-01-22 Geigy Ag J R Process for the production of phosphoric acid esters
US2630451A (en) * 1951-12-08 1953-03-03 American Cyanamid Co Dithiophosphate esters
DE876691C (en) * 1951-07-06 1953-05-18 Bayer Ag Process for the preparation of dithiophosphoric acid esters

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2266514A (en) * 1938-09-09 1941-12-16 American Cyanamid Co Esters of dithiophosphoric acids
DE819998C (en) * 1948-02-04 1951-11-08 American Cyanamid Co Process for the preparation of esters of phosphoric or thiophosphoric acid
DE833807C (en) * 1948-03-26 1952-03-13 American Cyanamid Co Process for the preparation of dithiophosphoric acid triesters
DE848041C (en) * 1949-07-13 1952-09-01 Borchers A G Geb Process for the preparation of esters of orthophosphoric acid and thiophosphoric acid
DE847897C (en) * 1950-03-02 1952-08-28 American Cyanamid Co Process for the preparation of dithiophosphoric acid triesters
DE864252C (en) * 1950-05-06 1953-01-22 Geigy Ag J R Process for the production of phosphoric acid esters
DE830508C (en) * 1950-05-24 1952-02-04 Bayer Ag Process for the preparation of neutral esters of thiophosphoric acid
DE876691C (en) * 1951-07-06 1953-05-18 Bayer Ag Process for the preparation of dithiophosphoric acid esters
US2630451A (en) * 1951-12-08 1953-03-03 American Cyanamid Co Dithiophosphate esters

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1032247B (en) * 1954-12-04 1958-06-19 Bayer Ag Process for the production of organic phosphorus compounds
DE1089376B (en) * 1958-02-12 1960-09-22 Bayer Ag Process for the preparation of thiophosphoric acid esters or thiophosphonic acid esters

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